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{"title":"Homogeneous Catalytic CO<sub>2</sub> Hydrogenationnby [Fe]-Hydrogenase Bioinspired Complexes: A Computational Study","authors":"VaniaM. Ramos (12315083), Antonio G. S. de Oliveira-Filho (12315086), Ana Paula de Lima Batista (3701710)","doi":"10.1021/acs.jpca.1c09761.s001","DOIUrl":"https://doi.org/10.1021/acs.jpca.1c09761.s001","url":null,"abstract":"Computational modeling at the DLPNO-CCSD­(T)/CBS//M06-L/def2-TZVPnlevel of theory was used to propose four different iron catalystsnwhose structures were inspired on the [Fe]-hydrogenase active site:n[Fe­(<sup>Me</sup>P<sup>N</sup>NH<sup>N</sup>P)­(acmp)] (<b>C­(1)</b>, <sup>Me</sup>P<sup>N</sup>NH<sup>N</sup>P = 2,6-bis­(dimethylphosphine),nacmp = acylmethylpyridine), [Fe­(C<sup>N</sup>NH<sup>N</sup>C)­(acmp)]n(<b>C­(2)</b>, C<sup>N</sup>NH<sup>N</sup>C = 2,6-bis­(methylimidazol-2-ylidene)),n[Fe­(<sup>Me</sup>P<sup>N</sup>N<sup>N</sup>P)­(acmp)] (<b>D­(1)</b>, <sup>Me</sup>P<sup>N</sup>N<sup>N</sup>P = 2,6-bis­((dimethylphosphine)­pyridine)),nand [Fe­(C<sup>N</sup>N<sup>N</sup>C)­(acmp)] (<b>D­(2)</b>, C<sup>N</sup>N<sup>N</sup>C = 2,6-bis­((methylimidazol-2-ylidene) pyridine)).nThrough these electronic structure calculations, the catalytic mechanismnof the reaction was explored. The intermediates and transition statesnpresent along the reaction coordinate were identified and describednas to their equilibrium geometries, vibrational frequencies, and energies.nQuasi-harmonic corrections were performed considering conditions analogousnto those used experimentally. To compare the catalytic activitiesnof the studied catalysts, turnover frequencies (TOFs) were calculated.nBased on the explored catalytic cycles and TOF values (<b>D­(1)</b> > <b>C­(1)</b> > <b>D­(2)</b> > <b>C­(2)</b>), thenmost suitable iron catalysts are those with tridentate phosphine pincer-typenligands coordinated to the metal center. These systems are new promisingniron catalysts to promote the CO<sub>2</sub> hydrogenation to formicnacid without any use of bases or additives.","PeriodicalId":521872,"journal":{"name":"Figshare","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2022-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147887172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}